Substituted hexahydroazepinecarboxylic amides

ABSTRACT

New and valuable substituted hexahydro-1H-azepine-1-carboxylic amides having a good herbicidal action and a process for controlling the growth of unwanted plants with these compounds.

United States Patent [19] Fischer et a].

[451 Aug. 28, 1973 SUBSTITUTED HEXAHYDROAZEPINECARBOXYLIC AMIDES [75] Inventors: Adolf Fischer, Mutterstadt;

Wolfgang Rohr, Mannheim; Walter-Wielant Wiersdorff, Ludwigshafen, Germany [73] Assignee: Badlsche Anllin- & Sodn-Fabrik Aktiengesellschaft, Land Rhineland-Pfalz, Germany 22 Filed: May 12, 1971 21 Appl.No.: 142,768

[30] Foreign Application Priority Data June 9, 1970 Germany P 20 28 168.9

[52] U.S. Cl. 260/239 BF, 71/88 OTHER PUBLICATIONS Rohr, Chem. Abstracts, Vol. 7i, Abstract No. 12389- 7w (1969). QDlASl.

Primary Examiner-Alton D. Rollins Att0rney.lohnston, Root, O'Keeffe, Keil, Thompson & Shurtleff [57] ABSTRACT New and valuable substituted hexahydro-lH-azepinel-carboxylic amides having a good herbicidal action and a process for controlling the growth of unwanted plants with these compounds.

5 Claims, No Drawings 1 SUBSTITUTED HEXAHYDROAZEPINECARBOXYLIC AMIDES The invention relates to new and valuable substituted methyl-hexahydro-lH-azepine-l-carboxylic amides for use as weedkillers and herbicides containing these compounds.

It is known to use N-m-trifluoromethylphenyl-N'- dimethylurea as a herbicide. However, its action is not satisfactory.

We have now found that hexahydro-lH-azepine-lcarboxylic aryl-amides of the formula where R denotes phenyl which may bear, as substituents, one or more identical or different halogen atoms (fluorine, chlorine, bromine, iodine), haloalkyl (trifluoromethyl, chloromethyl), alkyl (methyl, ethyl), alkoxy (methoxy, ethoxy, allyloxy, propargyloxy), alkylmercapto (methylmercapto), alkylsulfonyl (methylsulfonyl) or cyano groups, and Y denotes methyl or hydrogen, have a good herbicical action. This action is particularly effective on grass weeds and millet types.

The new herbicides are suitable for controlling unwanted plants in crops such as cotton, Indian corn and cereals at application rates of 1 to 4 kg per hectare.

The new compounds may be prepared by reacting an aryl isocyanate with a methylhexahydro-lH-azepine. The active ingredients may also be obtained by allowing a methylhexahydro-lH-azepine in the form of its l-acyl chloride to react with a suitable arylamine.

Methylhexahydro-lH-azepines are accessible for instance by reduction of the corresponding methylcaprolactams (cf. Amer. Chem. Soc., 76, 2317, 1954).

Examples of methylhexahydro-lH-azepines suitable for producing the active ingredients are as follows:

2-methylhexahydro-1H-azepine;

3-methylhexahydro- 1 H-azepine; 4-methylhexahydro-lH-azepine.

Mixtures containing the three individual structurally isomeric methylhexahydro-lH-azepines are also suitable. For instance, a methylhexahydro-lH-azepine isomer mixture is suitable which is obtained by reducing an isomer mixture of methylcaprolactam in turn obtained by photooximation of methylcyclohexane and subsequent Beckmann rearrangement.

EXAMPLE 1 Preparation of methylhexahydrol H-azepinel carboxylic-m-methyl-phenylamide:

At room temperature (C), 13.3 parts (by weight) of m-methy-phenyl isocyanate was slowly added to a solution of 11.3 parts of an isomer mixture of methylhexahydro-lH-azepine in 200 parts of benzene. The mixture was then stirred for 2 hours at 40C.

The benzene solution was washed with dilute hydrochloric acid and water, and dried. The product, after concentration in vacuo, melts at 86 to 88C.

The following compounds as isomer mixtures may be prepared analogously: methylhexahydro-l H-azepine- 1 -carboxylic-pfluorophenylamide,

m.p. 108 to 110C;

2 methylhexahydrol -H-azepinel -carboxylic-mtrifluoromethylphenyl-amide, m.p. 84 to 85C; methylhexahydrol H-azepine- 1 -carboxylic-3-chloro-4- bromophenyl-amide, m.p. 141 to 142C; methylhexahydro-l H-azepinel -carboxylic-3-chloro-4- methylmercapto-phenylamide; methylhexahydro- 1 H-azepinel -carboxylic-3-chloro-4- methoxyphenyl-amide, m.p. 104 to C; methylhexahydrol H-azepinel -carboxylic-3 ,4- dichlorophenylamide, m.p. 148 to 150C.

The agents according to the invention may be used as solutions, emulsions, suspensions or dusts. The form of application depends entirely on the purpose for which the agents are being used; in any case it should ensure a fine distribution of the active ingredient.

For the preparation of solutions to be sprayed direct, hydrocarbons having boiling points higher than 150C, e. g. tetrahydro-naphthalene or alkylated naphthalenes, or organic liquids having boiling points higher than 150C and having one or more than one functional group, e. g., the keto' troup, the ether group, the ester group or the amide group, this group or these groups being attached as substituent(s) to a hydrocarbon chain or being a component of a heterocyclic ring, may be used as spray liquids.

Aqueous formulations may be prepared from emulsion concentrates, pastes or wettable powders by adding water. To prepare emulsions the ingredients as such or dissolved in a solvent may be homogenized in water or organic solvents by means of wetting or dispersing agents, e. g., polyethylene oxide adducts. Concentrates which are suitable for dilution with water may be prepared from active ingredient, emulsifying or dispersing agent and possibly solvent.

Dusts maybe prepared by mixing or grinding the active ingredients with a solid carrier, e. g., kieselguhr, talc, clay or fertilizers.

The following examples demonstrate the use of the new active ingredients.

EXAMPLE 2 Loamy sandy soil was filled into pots and sown with Gossypium hirsutum, Poa annua, Poa trivialis, Echinochloa crus-galli, Lamium amplexicaule and Sinapis arvensls.

The soil prepared in this manner was immediately treated with 2 kg per hectare of an isomer mixture of methylhexahydro- 1 H-azepinel -carboxylic-pfluorophenylamide (1), with 2 kg per hectare of an isomer mixture of methylhexahydro-lH-azepine-lcarboxylic-m-methyl-phenylamide (11), with 2 kg per hectare of an isomer mixture of methylhexahydro-IH- azepine-1-carboxylic-m-trifluoromethylphenylamide (111) and, for comparison, with 2 kg per hectare of N- m-trifluoro-methylphenyl-N' ,N '-dimethylurea (IV), each active ingredient being dispersed in 500 liters of water per hectare.

After 4 to 5 weeks I, I1 and III had a stronger herbicidal action on weeds than 1V, combined with the same good compatibility with Gossypium hirsutum.

The results of the experiment are given in the following table.

Active ingredient 1 II Crop plant:

Gossypium hirsutum 0 0 0 Unwanted plants: Poa annua 100 95 I00 90 Pan trivlblis 95 90 95 85 Echinochloa crus-galli 100 90 I00 80 Laminum amplexicaule I00 95 I00 90 Sinapu'; arvensis 100 95 I00 90 0;- no damage 100 complete destruction.

EXAMPLE 3 The plants Gossypium hirsutum, Digitaria sanguinalis, Echinochloa crus-galli, Poa annua, Poa trivaiis and Lamium amplexicaule were treated at a growth height of 2 to 14cm with [.5 kg per hectare of an isomer mixture of methylhexahydrodl-l-azepine-lcarboxylic-p-fluorophenylamide (l), with l.5 kg per hectare of an isomer mixture of methylhexahydro-ll-lazepinel -carboxylic-m-methylphenylamide (ll), with 1.5 kg per hectare of an isomer mixture of methylhexahydrol l-l-azepine- 1 -carboxylic-m-trifluoromethylphenylamide (Ill) and, for comparison, with 1.5 kg per hectare of N-m-trifluoromethylphenyl-N',N'- dimethylurea (IV), each active ingredient being dispersed in 500 liters of water per hectare.

The results of the experiment after 4 weeks (considerable damage to Gossypium hirsutum by active ingredient IV) are given in the following table:

Active ingredient III IV Crop plant: Gossypium hirsutum 5 20 Unwanted plants: Digimria sanguimlis 100 95 95 85 Echinochloa crus-galli 100 95 100 90 Pm annua [00 95 95 80 P00 ln'vl'alis 100 100 95 80 Lamium amplexicaule I00 100 I00 100 0 no damage 100 complete destruction.

The action of the following compounds corresponds to that of I, ll and lll: methylhexahydro-l H-azepinel -carboxylic-3-chloro-4- methylmercaptophenylamide; methylhexahydro-l l-l-azepine- 1 -carboxylic-3-chloro-4- methoxyphenyl-amide; methylhexahydro- 1 l-l-azepine- I -carboxylic-3-chloro-4- bromophenyl-amide; and methylhexahydro-l H-azepinel -carboxylic-3 ,4- dichlorophenylamide.

EXAMPLE 4 90 parts by weight of compound I is mixed with parts by weight of N-methyl-a-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.

EXAMPLE 5 parts by weight of compoundll is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid-N- monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 6 20 parts by weight of compound lll is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanoi, 20 parts by weight of the adduct of 7 moles of ethylene oxide to 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 7 20 parts by weight of compound 1 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 8 20 parts by weight of compound II is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-a-sulfonic acid, 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquid is obtained containing 0.1% by weight of the active ingredient.

EXAMPLE 9 3 parts by weight of compound lll is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient. 7

EXAMPLE l0 UNITED STATES PATENT @FHCE 1} CERTIFICATE Cl QQRREQIION Patent No, q gwgr ggg Dated August 28 1913 Inventor(s) Ad f E1 sghexg e1; all

It is certified that error appears in the above-identified patent and that said Letters Patent arehereby corrected as shown below:

First page, lefthand column, please correct address of Assignee I 75 Assignees Badische Anilin- 8c Soda-Fabrik Aktiengeeellechaft, Ludwigshafen/Rhein,

Germany Column 1, Line 2 4-25, Delete "or hydrogen";

Column 2, line 23, "troup" should read group Column 3, line 4, "Laminum" should read Lamium Column 3, line 10, "trivalis" should read trivialis Column 3, line 27, column 1, "III" should read I Column 3, line 27, column 2, insert II-H Column 3, line 28 column 1, "05" should read 5 Column 3, line 28, column 2, insert O Column 4, line 46, delete "been eprayed Column 4, line 48, "beensprayed" should read been sprayed Signed and sealed this 5th day of November 1974.

LSEAL) Attest;

MCCOY n. GIBSCN JR. c. MARSHALL DANN Attesrlng Offlcer Commissioner of Patents ORM PO-1050 (10-69) uscoMM-oc come-P60 Q U. 5. GOVERNMENT PRINTING OFFICE I969 0-366334, 

2. Methylhexahydro-1H-azepine-1-carboxylic-m-methylphenylamide.
 3. Methylhexahydro-1H-azepine-1-carboxylic-m-trifluoromethyl-phenylamide.
 4. Methylhexahydro-1H-azepine-1-carboxylic-3-chloro-4-methyl-thiophenylamide.
 5. Methylhexahydro-1H-azepine-1-carboxylic-3-chloro-4-methoxy-phenylamide. 